JPH04211449A - Thermosetting resin composition and electronic part made thereof - Google Patents

Abstract

PURPOSE:To provide the subject composition containing an allylated polyhydric phenol and a specific polymaleimide compound, having excellent moldability and heat-resistance and useful for electronic parts, various electrical insulation materials, etc. CONSTITUTION:The objective composition can be produced by compounding (A) a compound of formula (the substituents R<1> to R<6> are H or 1-6C alkyl; the substituents R<7> to R<12> are H, 1-4C alkyl or 1-4C alkoxy; Xa to Xe are H, Cl or Br; n is 0-5) produced by allyl etherifying a polyhydric phenol produced by condensing (i) 1mol of an aromatic carbonyl compound (preferably p- hydroxybenzaldehyde) with (ii) 0.5-10mol of a phenolic compound in the presence of an acidic catalyst for novolak synthesis at 30-180 deg.C with (B) an N,N'- bismaleimide compound such as N,N'-diphenylmethane bismaleimide. The obtained objective composition contains the allylation product of the above polyhydric phenol and a polymaleimide compound having >=2 maleimide groups in one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermosetting resin composition, and more specifically to a thermosetting resin composition having excellent processability and heat resistance, and a thermosetting resin composition using the same. Regarding the electronic components obtained. [0002] Thermosetting resins are used as casting, impregnating, laminating, and molding materials in various electrical insulating materials, structural materials, adhesives, and the like. In recent years, the conditions for using materials in each of these applications have tended to become stricter, and in particular, the heat resistance of materials has become an important characteristic. Thermosetting polyimide resins have conventionally been used for such purposes, but in terms of processability, they require heating at high temperatures for long periods of time. In addition, although epoxy resins with improved heat resistance have excellent processability, they are insufficient in high heat resistance performance such as mechanical properties at high temperatures, electrical properties, and long-term heat deterioration resistance. [0003] As one of the materials to replace these, for example,
Thermosetting mixtures containing polyimides and alkenylphenols and/or alkenylphenol ethers (
JP-A-52-994), a heat-resistant resin composition containing a maleimide compound, a polyallylated phenol-based compound, and an epoxy resin (JP-A-53-134099) have been proposed. [0004] Problems to be Solved by the Invention [0004] However, since the polyallylated phenol compound used here is made from a bicyclic compound or a phenol novolac, etc., the bicyclic compound, which is a volatile component, Because it contains allyl ether or its Claisen rearrangement product, it tends to remain unreacted during heat curing or even after curing, causing problems in moldability, cured physical properties at high temperatures, heat deterioration resistance, etc. [Means for Solving the Problems] Against this background, the present inventors have conducted extensive studies on resin compositions that have excellent heat resistance and processability, and have found that a specific resin and maleimide compound The present inventors have discovered that a resin composition containing the following is suitable for the above purpose, and have completed the present invention. That is, the present invention provides (A) the following general formula [1
] [In the formula, substituents R1 to R6 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and substituents R7 to R12 are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. ~4
is an alkoxy group, Xa to Xe each independently represent a hydrogen atom, a chlorine atom or a bromine atom, and the average number of repeating units n is a number from 0 to 5. ) Allylated polyhydric phenol represented by (B
) A thermosetting resin composition characterized by containing a polymaleimide compound having two or more maleimide groups in the molecule, and a silicone resin having a specific structure blended into the thermosetting resin composition. The present invention provides a thermosetting resin composition characterized by: [0007] Furthermore, detailed explanations of each component in the present invention will be added below. In general formula [1], R1
, R2, R3, R4, R5 and R6 include hydrogen atom, methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, etc., with hydrogen atom and methyl group being particularly preferred. , ethyl group,
Mention may be made of propyl and butyl groups. Also, R7,
Specific examples of R8, R9, R10, R11 and R12 include hydrogen atom, methyl group, ethyl group, propyl group, butyl group, and methoxy group, preferably hydrogen atom, methyl group, and methoxy group, and particularly preferably It is a hydrogen atom. Further, Xa to Xe are particularly preferably hydrogen atoms. The larger n is, the more preferable it is from the point of view of heat resistance, but if it becomes too large, the melt viscosity will increase and the operability, moldability, etc. will decrease, so it is preferably 5 or less. The polyhydric phenol represented by the general formula [1] of the present invention is, for example, the general formula [4] [Chemical formula 5] (wherein, R corresponds to R11 and R12 of the general formula [1],
R', R'' are R7, R8, R9 of general formula [1]
, R10, and Y corresponds to Xb and Xd in general formula [1]. ) is obtained by the condensation of an aromatic carbonyl compound represented by phenol. Specific examples of the aromatic carbonyl compounds include hydroxybenzaldehyde, methylhydroxybenzaldehyde, dimethylhydroxybenzaldehyde, methoxyhydroxybenzaldehyde, chlorohydroxybenzaldehyde, bromobenzaldehyde,
Hydroxyacetophenone, hydroxyphenylethyl ketone, hydroxyphenylbutylketone, etc.
Hydroxybenzaldehydes, especially p-hydroxybenzaldehyde, are preferred. [0010] In combination with the aromatic carbonyl compound, other carbonyl compounds can also be used in small amounts. For example, formaldehyde, acetaldehyde, crotonaldehyde, acrolein, glyoxal, benzaldehyde, etc. Examples of phenols include phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, hexylphenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, methylphenylphenol, chlorophenol, bromophenol,
Examples include chlorocresol and bromocresol, with o-cresol being particularly preferred. The condensation of the aromatic carbonyl compound and the phenol is carried out at a temperature of 30 to 180°C at a ratio of about 0.5 to 10 moles of the phenol to 1 mole of the aromatic carbonyl compound.
The reaction is carried out in the presence of known acidic catalysts for novolac synthesis, such as mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as oxalic acid and toluenesulfonic acid, and salts such as zinc acetate. Note that an aromatic solvent such as toluene or chlorobenzene may be used at this time. Note that in order to increase the number of repeating units as an oligomer, it is sufficient to reduce the ratio of phenols, raise the temperature, and increase the amount of catalyst. The polyhydric phenols thus obtained can also be further halogenated with chlorine or bromine by a known method. Allyl etherification can also be obtained by a well-known method of converting phenols into allyl ether. That is, the condensate and allyl chloride, allyl bromide,
It is obtained by reacting allyl halide such as allyl iodide in the presence of an alkali such as caustic soda. Here, the alkali is used in an amount equivalent to that of the portion of the phenolic hydroxyl group desired to be allyl etherified. Further, the amount of allyl halide used is an amount equivalent to or more with respect to the alkali. The allyl etherification rate of the phenolic OH group is preferably 20 to 100%, more preferably 30 to 70%. Allylphenolization can be obtained by a method in which the above compound is rearranged by the action of heat (Claisen rearrangement). N,N'-bismaleimide compounds used in the present invention include N,N'-diphenylmethane bismaleimide, N,N'-phenylene bismaleimide, N,N'-diphenyl ether bismaleimide, N,N'-diphenyl ether bismaleimide,
, N'-diphenylsulfone bismaleimide, N,N'
-dicyclohexylmethane bismaleimide, N,N'-
Xylene bismaleimide, N,N'-tolylene bismaleimide, N,N'-xylylene bismaleimide, N,N
'-Diphenylcyclohexane bismaleimide (including isomers), N,N'-ethylene bismaleimide, N
, N'-hexamethylene bismaleimide, and these N
, N'-bismaleimide compound and a diamine, and the terminal thereof has an N,N'-bismaleimide core. In the resin composition of the present invention, especially allyl etherified polyhydric phenol has a low melt viscosity, so it is easy to mix with the bismaleimide resin and has excellent moldability. Furthermore, partially allyl etherified polyhydric phenol has a phenolic OH group and an allyl group, so it has high reactivity with bismaleimide resin and is suitable for sealing resins and the like. In the resin composition of the present invention, the aromatic nucleus-substituted allyl polyhydric phenol having Claisen rearrangement has a high melt viscosity, but a cured product having excellent toughness can be obtained. Furthermore, the partially aromatic-nucleically substituted allylated polyhydric phenol has rapid curing properties and is suitable for molding materials. In the resin composition of the present invention,
The quantitative ratio of the partially allyl etherified substituted phenolic novolac resin and the N,N'-bismaleimide compound is preferably selected such that the ratio of the double bonds of the latter to the double bonds of the former is 2 or less. If it exceeds 2, the content of unreacted allyl groups in the cured product increases, which is not preferable. Here, the N,N'-bismaleimide compound may be reacted with the allyl group in advance to such an extent that gelation does not occur. The silicone resin used in the present invention is represented by the following general formula [2] or [3]. [0016] (R1 and R2 each independently represent a methyl group or a phenyl group, R3 represents a functional group containing a hydrogen atom, an amino group, a glycidyl group or an alicyclic epoxy group,
l represents a number from 0 to 500, and m represents a number from 1 to 500. ) [0
embedded image (R1 and R2 each independently represent a methyl group or a phenyl group, R3 represents a functional group containing a hydrogen atom, an amino group, a glycidyl group, or an alicyclic epoxy group,
p represents a number from 0 to 500. ) Since the formula [2] tends to gel, the formula [3] is preferable. Number of repeating units, l, m and p
is more preferably 0 to 150. Furthermore, two or more of these silicone resins may be used in combination. As a silicone resin in which R3 is a hydrogen atom, X-21-7628 manufactured by Shin-Etsu Chemical Co., Ltd.
Examples include X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd. or Dow Corning Toray Silicone Co., Ltd., where R3 is a functional group containing an amino group (hereinafter referred to as amino group-containing silicone resin). Manufactured by SF-84
Examples include BX16-855B and B manufactured by Dow Corning Toray Silicone Co., Ltd., where R3 is a functional group containing a glycidyl group or an alicyclic epoxy group (hereinafter referred to as epoxy group-containing silicone resin).
Examples include X16-854B. Although the molecular weight is not necessarily limited,
Those having a molecular weight of approximately 500 to 30,000, preferably those having a molecular weight of 500 to 10,000 are used. Although these silicone resins can be used by simply mixing them with the allylated polyhydric phenol (A) and the polymaleimide compound (B), it is preferable to mix them with the allylated polyhydric phenol (A) or the polymaleimide compound (B) in advance. (B)
It is preferable to react with The reaction between the hydrogen group-containing silicone resin and the allyl group in the allyl compound of polyhydric phenol, component (A), is a hydrosilylation reaction,
This can be easily carried out by using a platinum-based catalyst or the like according to a conventional method. [0020] Furthermore, the glycidyl group- or alicyclic epoxy group-containing silicone resin can be easily reacted with the hydroxyl group in the allyl compound of polyhydric phenol, which is component (A), in the presence of a basic catalyst (for example, triethylamine, etc.). . Moreover, the amino group-containing silicone resin can be easily reacted with the maleimide group of bismaleimide, which is the component (B) in the composition of the present invention. By performing these reactions, it is possible to prevent silicone from bleeding from the cured product and to obtain a low stress thermosetting resin composition in which silicone is morphologically uniformly dispersed in the cured product. The quantitative proportion of the silicone resin is 3 to 30% of the total weight of the resin components (allylated polyhydric phenol (A) + polymaleimide compound (B) + silicone resin).
%. If the amount is less than this, the stress-lowering effect will be poor, and if it is more than this, the curability and heat resistance will decrease, so it is not preferable. Furthermore, the allylated polyhydric phenol, silicone-modified product, and polymaleimide resin in the composition of the present invention can be preliminarily reacted to form a prepolymer. As a result, moldability becomes even better, and a cured product that is morphologically uniform can be obtained, making it possible to further enhance the features of the present invention. Regarding the method of thermal curing of the resin composition of the present invention, it is possible to easily cure the resin composition without a catalyst, but it is possible to cure it even more easily by using a curing accelerator. Examples of such catalysts include triphenylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine,
Organic phosphine compounds such as tributylphosphine, trioctylphosphine, tri-2-cyanoethylphosphine, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide Radical polymerization initiators such as oxide, t-butyl hydroperoxide, azobisisobutyronitrile, etc., tertiary amines such as tributylamine, triethylamine, triamylamine, benzyltriethylammonium chloride, benzyltrimethylammonium hydroxide, etc. Examples include, but are not limited to, quaternary ammonium salts, imidazoles, boron trifluoride complexes, and transition metal acetylacetonates. Among these, organic phosphine compounds and imidazoles are particularly preferred. [0023] Furthermore, in order to control the curing rate, it is also possible to use a known polymerization inhibitor. For example, 2
, 6-di-t-butyl-4-methylphenol, 2,2
'-Methylenebis(4-ethyl-6-t-butylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-
6-t-butylphenol), hydroquinone monomethyl ether, and polyhydric phenols such as hydroquinone, catechol, pt-butylcatechol, 2,5-di-t-butylhydroquinone, methylhydroquinone, t-butylhydroquinone, and pyrogallol. Examples include phenols, phenothiazine compounds such as phenothiazine, benzophenothiazine, and acetamidophenothiazine, and N-nitrosamine compounds such as N-nitrosodiphenylamine and N-nitrosodimethylamine. Known epoxy resins and epoxy curing agents may be used in combination with the resin composition of the present invention. To give examples of these, epoxy resins include phenol,
Novolac epoxy resins derived from novolac resins, which are reaction products of phenols such as o-cresol and formaldehyde, phloroglycine, tris-(4-
Glycidyl ether compounds derived from trivalent or higher phenols such as hydroxyphenyl)-methane and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, bisphenol A, bisphenol F, hydroquinone, resorcinol, etc. diglycidyl ether compounds derived from functional phenols or halogenated bisphenols such as tetrabromobisphenol A, p-aminophenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4'- Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3
, 4'-diaminodiphenyl ether, 1,4-bis(
4-aminophenoxy)benzene, 1,4-bis(3-
aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)propane, p-phenylenediamine, m
-phenylenediamine, 2,4-toluenediamine, 2
, 6-toluenediamine, p-xylylenediamine, m
-xylylene diamine, 1,4-cyclohexane bis(
amine-based epoxy resin derived from methylamine), 1,3-cyclohexanebis(methylamine), etc.
- Glycidyl ester compounds derived from aromatic carboxylic acids such as oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, and isophthalic acid, hydantoin epoxy resins derived from 5,5-dimethylhydantoin, etc., 2
, 2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)
cyclohexyl]propane, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3
, 4-epoxycyclohexanecarboxylate, and N,N-diglycidylaniline, and one or more of these epoxy resins are used. Also, known epoxy resin curing agents can be used, such as novolac resins such as phenol novolak and cresol novolac, aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone, pyromellitic anhydride and benzophenone tetracarboxylic anhydride. Examples include acid anhydrides such as acids, but are not limited thereto. In the present invention, an inorganic filler can also be added. Examples of fillers that can be used include silica powder, alumina, talc, calcium carbonate, titanium white, clay, asbestos, mica, red iron oxide, and glass fiber, with silica powder and alumina being particularly preferred. The blending ratio of the inorganic filler when used for encapsulating a semiconductor is preferably 25 to 90% by weight, more preferably 60 to 80% by weight based on the total amount of the resin composition. In the present invention, natural waxes, synthetic waxes, higher fatty acids and their metal salts, release agents such as paraffin, coloring agents such as carbon black, and coupling agents may be added as necessary. It's okay. Additionally, flame retardants such as antimony trioxide, phosphorus compounds, and brominated epoxy resins may be added. The resin composition thus obtained can be compounded by melt-kneading it with a general kneader such as a roll or a co-kneader. The electronic component of the present invention can be heated to 160 to 200°C using this compound.
It can be easily produced by transfer molding or compression molding at a certain temperature. Further, the thermosetting resin-assembled copper-clad laminate, which is one of the electronic components of the present invention, can be manufactured according to a known method. For example, a base material is impregnated with a resin varnish obtained by dissolving the above resin composition in an organic solvent, heat-treated to obtain a prepreg sheet, and the prepreg sheet is laminated with copper foil and heat laminated to form a copper-clad laminate. A board is obtained. Examples of the solvent include methyl ethyl ketone, ethylene glycol monomethyl ether, N,N-dimethylformamide, and N-methyl-2-pyrrolidone. Examples of the base material include woven fabrics, nonwoven fabrics, mats, or paper made of inorganic or organic fibers such as glass fibers, polyester fibers, and polyamide fibers, or combinations thereof. The heat treatment conditions also depend on the solvent used, catalyst,
It can be appropriately selected depending on the type and amount of additive. The heating molding conditions are a temperature of 150 to 250°C,
An example is press molding for 20 to 300 minutes under a pressure of 10 to 100 kg/cm2. Effects of the Invention As explained above, the thermosetting resin composition of the present invention provides a cured product with excellent processability and excellent heat resistance, and furthermore, the electronic component obtained using the same has the following properties: Compared to conventionally known products, it has extremely superior heat resistance, dimensional stability, low stress properties, and adhesive properties, and its industrial value is great. [Example] The present invention will be explained in more detail with reference to Examples below. The functional group-containing silicone resins used in Examples are as follows. [Chemical formula 8] [Chemical formula 9] [Chemical formula 10] Reference example 1 (Synthesis of raw material polyhydric phenol) In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 431.6 g (4 equivalents) of o-cresol, 122.1 g (1 equivalent) of p-hydroxybenzaldehyde, p-
After charging 3.0 g of toluenesulfonic acid and 872 g of n-heptane as a reaction solvent and completely dissolving the resin, the temperature was raised to 105° C. to perform azeotropic dehydration. After incubating at 105° C. for 7 hours, the system is cooled to room temperature. The reaction product precipitated by cooling was separated by filtration, dissolved in 2895 g of methanol at room temperature, washed with water, and then dried under reduced pressure at 80° C. for 24 hours to form a reddish brown powder with an OH equivalent of 110.9 g/eq.
5g was obtained. (It is referred to as TPM-1.) Reference Example 2 (Synthesis of allyl ether compound) The polyhydric phenol TPM obtained in Reference Example 1 was placed in a reactor equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser. -1 to 1
20 g (1.08 equivalent) and 420 g of dimethyl sulfoxide as a reaction solvent are charged, and after the resin is completely dissolved, 21.9 g (0.54 equivalent) of 99% caustic soda is added and stirred well. While maintaining the temperature of the reaction system at 40°C, 43.6 g (0.56 equivalents) of allyl chloride was added dropwise over 1 hour, and then the temperature was raised to 50°C and maintained at the same temperature for 5 hours. Then, after distilling off the dimethyl sulfoxide, 600 g of methyl isobutyl ketone was charged, the resin was dissolved, and the inorganic salts were removed by washing with water and filtration, and the filtrate was concentrated to obtain an allyl etherification rate of 50%, which does not have a nuclear substituted allyl group. OH
132.6 g of a reddish brown semi-solid resin with an equivalent weight of 262 g/eq was obtained. (It is referred to as ALN-1.) Reference Example 3 (Synthesis of allyl ether compound) Polyhydric phenol TPM-1 of Reference Example 2 120 g (1
．． The reaction was carried out in exactly the same manner as in Reference Example 2, except that 420 g of dimethyl sulfoxide was changed to 210 g, 600 g of methyl isobutyl ketone was changed to 300 g, and the reaction did not have a nuclear substituted allyl group. 76.3 g of a reddish brown semi-solid resin with an allyl etherification rate of 100% and an OH content of 0.2% was obtained. (Set as ALN-2.) 0
Reference Example 4 (Synthesis of raw material polyhydric phenol) 215.8 g (2 equivalents) of o-cresol, 122 g (1 equivalent) p-hydroxybenzaldehyde, 3.0 g p-toluenesulfonic acid, and 528 g n-heptane were charged. The reaction was carried out by azeotropic dehydration at 105°C for 7 hours in the same manner as in Reference Example 1, and the reaction product was filtered, then dissolved in 1148 g of methyl isobutyl ketone, washed with water, and after separation, the oil layer was concentrated. Accordingly, OH equivalent 125.9g
249.0 g of reddish brown semi-solid resin of /eq was obtained. (TP
Let it be M-2. ) Reference Example 5 (Synthesis of allyl ether compound) The polyhydric phenol TPM-2 obtained in Reference Example 4 was
g (1.112 equivalents), 322 g of dimethyl sulfoxide as reaction solvent, 22.2 g of 99% caustic soda (0.5
56 equivalents) and 44.8 g (0.586 equivalents) of allyl chloride were charged, and the reaction was carried out in exactly the same manner as in Reference Example 2, resulting in an allyl etherification rate of 50% (1H
-Calculated from the number of aromatic protons and allyl group protons in NMR. 140.6 g of reddish brown semi-solid resin of ) was obtained. (It is referred to as ALN-3.) Reference Example 6 (Synthesis of raw material polyhydric phenol) 656.8 g of 2-t-butyl-5-methylphenol (
4 equivalents), p-hydroxybenzaldehyde 122.1
g (1 equivalent), p-toluenesulfonic acid as catalyst 3.
0 g and 1,300 g of n-heptane as a reaction solvent, the reaction was carried out in the same manner as in Reference Example 1, and the reaction product precipitated by cooling was filtered, dissolved in 4,400 g of methanol, treated in the same manner as in Reference Example 1, and OH Equivalent weight 144.1g/e
367.5 g of a reddish brown semi-solid resin of q was obtained. (TPM-
3. ) Reference Example 7 (Synthesis of allyl ether compound) Polyhydric phenol TPM-3 obtained in Reference Example 6 was mixed with 70.
0 g (0.487 equivalent), 161 g of dimethyl sulfoxide as reaction solvent, 9.84 g (0.487 eq.) of 99% caustic soda.
246 equivalents), and 19.8 g (0.25 equivalents) of allyl chloride
9 equivalents) and carried out the reaction in exactly the same manner as in Reference Example 2, resulting in an allyl etherification rate of 60% (
Calculated from the number of aromatic protons and allyl group protons in 1H-NMR. ) 71.9 g of this reddish brown semi-solid resin was obtained. (It is referred to as ALN-4.) Reference Example 8 (Synthesis of raw material polyhydric phenol) The charged amount of 2-t-butyl-5-methylphenol of Reference Example 6, 656.8 g (4 equivalents), was added to 328.4 g. (2 equivalents)
The reaction was carried out in the same manner as in Reference Example 4 except for the O
Reddish brown semi-solid resin with H equivalent of 140.0 g/eq 293.
2g was obtained. (It is referred to as TPM-4.) Reference Example 9 (Synthesis of allyl ether compound) The polyhydric phenol TPM-4 obtained in Reference Example 8 was
．． 0 g (0.714 equivalents), 230 g of dimethyl sulfoxide as reaction solvent, 14.4 g of 99% caustic soda (0.0
．． 361 equivalents) and allyl chloride 29.1 g (0.380
(equivalent amount) was prepared in exactly the same manner as in Reference Example 2, and the reaction was carried out,
Allyl etherification rate 4 without nuclear substitution allyl ether
8% (calculated from the number of aromatic protons and allyl group protons in 1H-NMR) reddish brown semi-solid resin 105.0
I got g. (It is referred to as ALN-5.) Reference Example 10 (Synthesis of raw material polyhydric phenol) 492.6 g of 2-t-butyl-5-methylphenol (
3 equivalents), m-cresol 108g (1 equivalent), p-hydroxybenzaldehyde 122.1g (1 equivalent)
, 3.0 g of p-toluenesulfonic acid and 528 g of n-heptane were charged in the same manner as in Reference Example 1, the reaction was carried out, and the reaction product was treated in exactly the same manner as in Reference Example 4.
．． 394.7 g of a reddish-brown semisolid resin product of 6 g/eq was obtained. (It is referred to as TPM-5.) Reference Example 11 (Synthesis of allyl ether compound) The polyhydric phenol TPM-5 obtained in Reference Example 10 was
0.0g (0.760 equivalent), 230g of dimethyl sulfoxide as reaction solvent, 15.4g of 99% caustic soda (
0.384 equivalents), and 30.9 g (0.4 equivalents) of allyl chloride
04 equivalent) was charged in exactly the same manner as in Reference Example 2, and the reaction was carried out, resulting in an allyl etherification rate of 37% (calculated from the number of aromatic protons and allyl group protons in 1H-NMR) with no nuclear substituted allyl ether. reddish brown semi-solid resin 10
7g was obtained. (Defined as ALN-6.) Reference Example 12 [Silicone Modification] 100 g of ALN-1 obtained in Reference Example 2 and a platinum catalyst (
2 g of 1% Pt-containing platinum black) and 331 g of xylene as a reaction solvent were charged, and after completely removing water from the system by azeotropic dehydration, the silicone resin (a) was added under reflux of xylene.
After dropping 28.1 g over about 1 hour, the mixture was kept warm under xylene reflux for about 5 hours. Next, this solution was filtered to completely remove the platinum catalyst, and the filtrate was concentrated to obtain a silicone modified product. (Described as modified product-(a).) Reference Example 13 [Silicone modification] N,N'-diphenylmethane bismaleimide (hereinafter referred to as BM
100 g of silicone resin (b) and 369 g of 1,4-dioxane as a reaction solvent were charged, the temperature was raised to 100°C to completely dissolve BMI, and 58 g of silicone resin (b) was added dropwise over about 1 hour. Hold for 1 hour. Dioxane was then distilled off to obtain a modified silicone product (referred to as modified product-(b)). Reference Example 14 [Silicone Modification] 100 g of ALN-1 obtained in Reference Example 2, 5 g of triethylamine, and 331 g of xylene as a reaction solvent were charged, and the temperature was raised to 140° C. to completely dissolve the resin. After dropping 28.1 g of silicone resin (c) over about 1 hour, this temperature was maintained for about 15 hours. Then, xylene and triethylamine were distilled off to obtain a silicone modified product (
Modified product-(c)). Reference Example 15 [Silicone Modification] 100 g of ALN-3 obtained in Reference Example 5, 5 g of triethylamine, and 331 g of xylene as a reaction solvent were charged, and the temperature was raised to 140° C. to completely dissolve the resin. After dropping 25.9 g of silicone resin (d) over about 1 hour, this temperature was maintained for about 20 hours. Then, xylene and triethylamine were distilled off to obtain a silicone modified product (
Modified product-(d)). Examples 1 to 11 Allylated products of polyhydric phenols obtained in reference examples, silicone modified products (a) to (d) and BMI are shown in Table-1 and Table-
Blend in the proportions shown in 2, heat and melt mix at about 130°C,
After maintaining this temperature for 30 minutes, it was immediately cooled to obtain each prepolymer. The obtained prepolymer, curing accelerator, filler, coupling agent, and mold release agent were melt-kneaded using heated rolls at 50 to 120°C for 5 minutes according to the formulations shown in Tables 1 and 2. After cooling, each resin composition was obtained by pulverization. Next, these compositions were heated at 175°C x 7
Transfer molding was carried out under conditions of 0 kg/cm2 x 3 minutes, post-curing was performed at 200°C for 5 hours, and then physical properties were evaluated. The results are shown in Tables 3 and 4. Comparative Example 1 O-cresol novolac type epoxy resin (epoxy equivalent: 195 g/eq), phenol novolac resin (OH
A resin composition was obtained by kneading a curing accelerator, a filler, a mold release agent, and a coupling agent according to the formulation shown in Table 2 in the same manner as in the examples. Next, this was transfer molded under the conditions of 175° C. x 70 kg/cm 2 x 5 minutes, and after post-curing at 180° C. for 5 hours, the physical properties were evaluated. The results are shown in Table-4. Examples 12 to 19 Allylated polyhydric phenols obtained in reference examples and BMI
and 150℃~
Melt and mix by heating at 160°C and stirring for 10 to 20 minutes.
A prepolymer having a viscosity of 6 to 7 poise at 150° C. was obtained by keeping the temperature for a minute. 60 parts by weight of this prepolymer was added to N, N
-N,N' dissolved in 40 parts by weight of dimethylformamide
- A resin varnish without precipitation of diphenylmethane bismaleimide was obtained. The varnish was coated with glass cloth (Kanebo Co., Ltd.)
S-1600, aminosilane treatment), impregnated with 160
A prepreg was obtained by heat treatment in an oven for 10 to 20 minutes. 6 sheets of prepreg and copper foil (Furukawa Circuit Foil)
Co., Ltd. TTAI treatment, 35 μ thick) layered at 200℃, 50k
Press molded for 2 hours at a pressure of g/cm2 to a thickness of 1m.
A copper-clad laminate with a thickness of m was obtained. The physical properties of this laminate are determined by JIS-
It was measured according to C-6431, and the results shown in Tables 5 and 6 were obtained. For measuring the bending strength at 240° C., a 1.6 mm thick laminate formed by molding the 8 prepregs described above under the same conditions was used. Comparative Example 2 60 parts by weight of Kerimid (registered trademark)-601 (manufactured by Rhône-Poulenc) was mixed with 4 parts by weight of N,N-dimethylformamide.
The varnish obtained by dissolving 0 parts by weight was impregnated into a glass cloth in the same manner as in the example, heat treated to prepare a prepreg,
Press molding was performed at 0° C. and 50 kg/cm 2 for 2 hours to obtain a copper-clad laminate. The physical properties of this laminate are shown in Tables 5 and 6. [0054] The raw materials used in the Examples and Comparative Examples are described below. BMI; Bestlex (manufactured by Sumitomo Chemical Co., Ltd.)
Registered trademark) BH-180 ESCN195XL; manufactured by Sumitomo Chemical Co., Ltd. o-cresol novolac type epoxy resin (epoxy equivalent: 19
5g/eq) Phenol novolak resin; OH equivalent 110g/eq
Softening point 90°C Silane coupling agent-A; manufactured by Shin-Etsu Silicone Co., Ltd.
KBM-573 〃 -B: SH-6040 fused silica manufactured by Toray Dow Corning Silicone Co., Ltd.; FS-891 spherical fused silica manufactured by Denki Kagaku Kogyo Co., Ltd.; 〃 FB-90
The evaluation methods for the various physical properties listed in Tables 3, 4, 5 and 6 are as follows. Spiral flow: Standard EMMI 1-66 RE
Barcol hardness according to VISIONA: According to ASTM D2583-67 Glass transition temperature: According to TMA method (manufactured by Shimadzu Corporation)
(Using DT-40 pyrolysis equipment) Linear expansion coefficient: Based on TMA method (Shimadzu Corporation DT-
40 pyrolysis equipment) Thermal expansion coefficient: Based on TMA method (Shimadzu DT-4
0 pyrolysis device used) Soldering heat resistance: QFP 84pin, 34mmt, element 10 x 10mm, pressure cooker 121℃ x 10
After 0%RH x 24hr, immediately immerse in solder bath (260
×10 seconds) [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6]

Claims

[Claims] Claim 1: (A) The following general formula [1] [Formula 1] (wherein, substituents R1 to R6 are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, and substituents R7 to R12 are hydrogen atoms atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms
is an alkoxy group, Xa to Xe each independently represent a hydrogen atom, a chlorine atom or a bromine atom, and the average number of repeating units n is a number from 0 to 5. ) Allylated product of polyhydric phenol represented by (B)
A thermosetting resin composition comprising a polymaleimide compound having two or more maleimide groups in the molecule. 2. A thermosetting resin composition comprising the thermosetting resin composition of claim 1 and a silicone resin represented by the following general formula [2] or [3]. [Chemical formula 2] (R1 and R2 each independently represent a methyl group or a phenyl group, R3 represents a functional group containing a hydrogen atom, an amino group, a glycidyl group, or an alicyclic epoxy group,
l represents a number from 0 to 500, and m represents a number from 1 to 500. ), [Chemical 3] (R1 and R2 each independently represent a methyl group or a phenyl group, R3 represents a functional group containing a hydrogen atom, an amino group, a glycidyl group, or an alicyclic epoxy group,
p represents a number from 0 to 500. ) 3. An electronic component molded and sealed with a resin composition comprising the thermosetting resin composition of claim 1 or 2 and a filler. 4. A thermosetting product obtained by impregnating a base material with a resin varnish obtained by dissolving the thermosetting resin composition of claim 1 in an organic solvent and heat-treating the prepreg, which is then laminated with a copper foil and then heat-formed. Resin copper clad laminate.